Author, as appears in the article.: Hernández S; Ottone C; Proto S; Tolod K; Díaz De Los Bernardos M; Solé-Daura A; Carbó J; Godard C; Castillón S; Russo N; Saracco G; Claver C

Department: Química Física i Inorgànica Química Analítica i Química Orgànica

e-ISSN: 1463-9270

URV's Author/s: Carbó Martin, Jorge Juan / Castillón Miranda, Sergio / Claver Cabrero, Maria del Carmen Orosia / Godard, Cyril

Keywords: dye-sensitized semiconductor water splitting photocatalysis Naphtalenediimides

Abstract: In this work, a novel catalytic system for the sunlight-driven water splitting reaction, which exploits the photocatalytic ability of BiVO4 coupled to a new kind of noble-metal-free organic dye molecules, is proposed. Hence, mono- and di-substituted naphthalenediimides (NDIs) were designed to have different functional groups that provide to them both tunable optical properties and adjustable HOMO/LUMO levels, and were selectively prepared (starting from 1,4,5,8-naphthalenetetracarboxylic acid) achieving yields >69%. Smart anchoring groups (i.e. carboxylates or aromatic amines) were added to the dyes in order to allow them to covalently bond to acidic -OH groups present on the BiVO4 surface. An easy and low-cost room temperature dip-coating technique was used to dye-sensitize both BiVO4 powders and thin films. NMR, MS, FT-IR, TG, FESEM, XRD, XPS and optical analyses confirmed the successful organic synthetic routes and good dyes/BiVO4 linkages. Photochemical and photoelectrochemical water oxidation reaction tests, together with DFT calculations, demonstrated that a proper alignment of the semiconductor/NDI-based dye energy levels is fundamental for enhancing the photocatalyst performance through a Z-scheme mechanism. The ability of the NDI organic molecules to delocalize the electronic charges was also a key factor for minimizing recombination processes and achieving more than a ten-fold increase in the photocurrent density of a 6 cm2 BiVO4 photo-electrode. The here reported results open new perspectives for the utilization of this new series of core-substituted NDIs, which are able to improve the activity of photocatalysts for different sunlight-driven applications, e.g. waste water treatment and organic contaminants' degradation, other than the production of solar fuels by water splitting mechanisms

Thematic Areas: Química Pollution Medicina veterinaria Medicina ii Materiais Interdisciplinar Green & sustainable science & technology Farmacia Environmental chemistry Engenharias iv Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry Biotecnología Astronomia / física

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 1463-9262

Author's mail: carmen.claver@urv.cat sergio.castillon@urv.cat j.carbo@urv.cat cyril.godard@urv.cat

Author identifier: 0000-0002-2518-7401 0000-0002-0690-7549 0000-0002-3945-6721 0000-0001-5762-4904

Record's date: 2023-02-26

Papper version: info:eu-repo/semantics/acceptedVersion

Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2017/gc/c7gc00125h#!divAbstract

Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/

Papper original source: Green Chemistry. 19 (10): 2448-2462

APA: Hernández S; Ottone C; Proto S; Tolod K; Díaz De Los Bernardos M; Solé-Daura A; Carbó J; Godard C; Castillón S; Russo N; Saracco G; Claver C (2017). Core-substituted naphthalenediimides anchored on BiVO4 for visible light-driven water splitting. Green Chemistry, 19(10), 2448-2462. DOI: 10.1039/c7gc00125h

Article's DOI: 10.1039/c7gc00125h

Entity: Universitat Rovira i Virgili

Journal publication year: 2017

Publication Type: Journal Publications